We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Photoelectron spectroscopy revealed that a 20-atom gold cluster has an extremely large energy gap, which is even greater than that of C60, and an electron affinity comparable with that of C60. This observation suggests that the Au20 cluster should be highly stable and chemically inert. Using relativistic density functional calculations, we found that Au20 possesses a tetrahedral structure, which is a fragment of the face-centered cubic lattice of bulk gold with a small structural relaxation. Au20 is thus a unique molecule with atomic packing similar to that of bulk gold but with very different properties.

http://cluster.physik.uni-freiburg.de/lehre/SS11/ueb11/Li2003b.pdf

Au20: A Tetrahedral Cluster

/pdf/surface-chemistry-of-catalysis-by-gold-37hj5cal3q.pdf

Surface chemistry of catalysis by gold

Applications and validations of the Minnesota density functionals

Gold is an element whose unique properties are strongly influenced by relativistic effects. A large body of appropriate calculations now exists and its main conclusions are summarized in this critical review. The present paper completes the recent reviews by Pyykko (2004, 2005) (529 references).

Theoretical chemistry of gold. III

A combined experimental and theoretical study of small gold cluster anions is performed. The experimental effort consists of ion mobilitymeasurements that lead to the assignment of the collision cross sections for the different cluster sizes at room temperature. The theoretical study is based on ab initiomolecular dynamics calculations with the goal to find energetically favorable candidate structures. By comparison of the theoretical results with the measured collision cross sections as well as vertical detachment energies (VDEs) from the literature, we assign structures for the small Au n − ions (n<13) and locate the transition from planar to three-dimensional structures. While a unique assignment based on the observed VDEs alone is generally not possible, the collision cross sections provide a direct and rather sensitive measure of the cluster structure. In contrast to what was expected from other metal clusters and previous theoretical studies, the structural transition occurs at an unusually large cluster size of twelve atoms.

The structures of small gold cluster anions as determined by a combination of ion mobility measurements and density functional calculations

Structures of small silver cluster cations (Agn+, n<12): ion mobility measurements versus density functional and MP2 calculations

We present ion mobility measurements for small gold cluster cations, Aun+(n⩽10) in the temperature range between 77 and 300 K. While at room temperature all cluster sizes show only one sharp peak in the arrival time distribution, the Au9+ signal becomes bimodal at temperatures below 140 K. We interpret this unusual behavior in terms of two different isomeric forms of this ion which undergo temperature dependent interconversion reactions. From the reaction rate the activation barrier for this isomerization can be estimated to be 10–20 kJ/mol.

Thomas Bierweiler

Papers

The structures of small gold cluster anions as determined by a combination of ion mobility measurements and density functional calculations

Structures of small silver cluster cations (Agn+, n<12): ion mobility measurements versus density functional and MP2 calculations

Au9+: Rapid isomerization reactions at 140 K